Photosensitve polymide precursor and its use for pattern formation

Abstract

A polyimide precursor having repeating units of the formula: ##STR1## wherein R 1 is a tetravalent organic group having 4 or more carbon atoms; R 2 is a trivalent or tetravalent organic group having one or more aromatic rings; R 3 is a monovalent organic group; A is a monovalent group showing acidity; and n is an integer of 1 or 2, is effective for preparing a highly sensitive negative-working photosensitive material developable with an alkaline aqueous solution in a short time with high resolution.

What is claimed is: 
     
       1. A polyimide precursor having repeating units of the following formula (1) and a weight-average molecular weight of 10,000 to 200,000: ##STR73## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  is (a) a group represented by the formula: ##STR74## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, or a combination of (a) and (b) an alkyl group having 1 to 6 carbon atoms; A is a monovalent group showing acidity; and n is an integer of 1 or 2. 
     
     
       2. A polyimide precursor according to claim 1, wherein A is at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid, a carboxylic acid group, and an hydroxyl group. 
     
     
       3. A polyimide precursor according to claim 2, wherein A is a carboxylic acid group. 
     
     
       4. A polyimide precursor according to claim 1, wherein R 1  is one member selected from the following formulae; ##STR75## 
     
     
       5. A polyimide precursor according to claim 1, wherein R 2  is one member selected from the following formulae: and Z is one member selected from the following formulae: --O--, --S--, --CO--, --SO 2  --, --CH 2  --, --C(CF 3 ) 2  --, ##STR76## 
     
     
       6. A polyimide precursor having repeating units of the following formulae (1) and (2) and a weight-average molecular weight of 10,000 to 200,000: wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  is (a) a group represented by the formula: ##STR77## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, or a combination of (a) and (b) an alkyl group having 1 to 6 carbon atoms; A is a monovalent group showing acidity; and n is an integer of 1 or 2; and ##STR78## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 3  is a monovalent organic group; and R 4  is a divalent organic group containing one or more aromatic rings or silicon atoms; wherein the number of repeating units of the formula (1) is 10 or more and the number of repeating units of the formula (2) is 90 or less when a total of the repeating units of the formulae (1) and (2) is 100. 
     
     
       7. A polyimide precursor according to claim 6, wherein A is at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid, a carboxylic acid group, and a hydroxyl group. 
     
     
       8. A polyimide precursor according to claim 6, wherein R 1  is one member selected from the following formulae: ##STR79## 
     
     
       9. A polyimide precursor according to claim 6, wherein R 2  is one member selected from the following formulae: and Z is one member selected from the following formulae: --O--, --S--, --CO--, --SO 2  --, --CH 2  --, --C(CF 3 ) 2  --, ##STR80##10. 
     
     
       10. A polyimide precursor according to claim 6, wherein R 3  is represented by the formula: wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R8 is a divalent organic group. 
     
     
       11. A polyimide precursor according to claim 10, wherein R 3  is represented by the formula: ##STR81## 
     
     
       12. A polyimide precursor according to claim 6, wherein R 3  in one molecule is represented by the formula: wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R8 is a divalent organic group, in an amount of 10 to 100% by mole, and the remainder is an alkyl group having 1 to 6 carbon atoms. 
     
     
       13. A polyimide precursor according to claim 6, wherein R 4  is one member selected from the following formulae: ##STR82## 
     
     
       14. A polyimide precursor according to claim 6, wherein R 3  is represented by the formula (5) and A is at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxylic acid group, and a hydroxyl group. 
     
     
       15. A polyimide precursor according to claim 6, wherein R 3  is represented by the formula (5) and R 1  is one member selected from the following formulae: 
     
     
       16. A polyimide precursor according to claim 6, wherein R 3  is represented by the formula (5) and R 2  is one member selected from the following formulae: ##STR83## and Z is one member selected from the following formulae: ##STR84## 
     
     
       17. A polyimide precursor according to claim 6, wherein R 3  in one molecule is represented by the formula: wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, in an amount of 10 to 100% by mole, and the remainder is an alkyl group having 1 to 6 carbon atoms; and A is at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxylic acid group, and a hydroxyl group. 
     
     
       18. A polyimide precursor according to claim 6, wherein R 3  in one molecule is represented by the formula: ##STR85## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, in an amount of 10 to 100% by mole, and the remainder is an alkyl group having 1 to 6 carbon atoms; and R 1  is one member selected from the following formulae: ##STR86## 
     
     
       19. A polyimide precursor according to claim 6, wherein R 3  in one molecule is represented by the formula: wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, in an amount of 10 to 100% by mole, and the remainder is an alkyl group having 1 to 6 carbon atoms; and R 2  is one member selected from the following formulae: ##STR87## and Z is one member selected from the following formulae: ##STR88##20. 
     
     
       20. A polyimide precursor having repeating units of the following formula (1) and a weight-average molecular weight of 10,000 to 200,000: wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  is a monovalent organic group represented by the formula: ##STR89## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group; A is a monovalent group showing acidity; and n is an integer of 1 or 2. 
     
     
       21. A polyimide precursor according to claim 20, wherein R 3  is represented by the formula: ##STR90## 
     
     
       22. A polyimide precursor according to claim 20, wherein A is at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid, a carboxylic acid group, and a hydroxyl group. 
     
     
       23. A polymide precursor according to claim 20, wherein R1 is one member selected from the following formulae: 
     
     
       24. A polyimide precursor according to claim 20, wherein R 2  is one member selected from the following formulae: and Z is one member selected from the following formulae: ##STR91## 
     
     
       25. A polyimide precursor having repeating units of the following formula (1) and a weight-average molecular weight of 10,000 to 200,000: wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  in one molecule is represented by the formula: ##STR92## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, in an amount of 10 to 100% by mole, and the remainder is an alkyl group having 1 to 6 carbon atoms; A is a monovalent group showing acidity; and n is an integer of 1 or 2. 
     
     
       26. A polyimide precursor according to claim 25, wherein A is at least one group selected from the group consisting of a slufonic acid group, a sulfinic acid group, a carboxylic acid group, and a hydroxyl group. 
     
     
       27. A polyimide precursor according to claim 25, wherein R 1  is one member selected from the following formulae: ##STR93## 
     
     
       28. A polyimide precursor according to claim 25, wherein R 2  is one member selected from the following formulae: and Z is one member selected from the following formulae: ##STR94## 
     
     
       29. A polyimide precursor composition comprising a polyimide precursor having repeating units of the formula: wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  is (a) a group represented by the formula: ##STR95## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, or a combination of (a) and (b) an alkyl group having 1 to 6 carbon atoms; A is a monovalent group showing acidity; and n is an integer of 1 or 2. 
     
     
       30. A polyimide precursor composition according to claim 29, wherein the polyimide precursor is contained in an amount of 100 parts by weight, together with 0.1 to 50 parts by weight of a photosensitizer, and 0.1 to 50 parts by weight of a photopolymerization auxiliarly agent. 
     
     
       31. A polyimide precursor composition according to claim 29, wherein the polyimide precursor further has repeating units of the formula: ##STR96## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 3  is a monovalent organic group; and R 4  is a divalent organic group containing one or more aromatic rings or silicon atoms, the number of repeating units of the formula (1) being 10 or more, and the number of repeating units of the formula (2) being 90 or less, when a total of repeating units of the formulae (1) and (2) is 100. 
     
     
       32. A polyimide precursor composition according to claim 31, wherein the polyimide precursor is contained in an amount of 100 parts by weight, together with 0.1 to 50 parts by weight of photosensitizer, and 0.1 to 50 parts by weight of a photopolymerization auxiliarly agent. 
     
     
       33. A polyimide precursor composition according to claim 29, wherein A is at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a carboxylic acid group and a hydroxyl group. 
     
     
       34. A polyimide precursor composition according to claim 33, wherein A is a carboxylic acid group. 
     
     
       35. A polyimide precursor composition comprising a polyimide precursor, having repeating units of the formula: ##STR97## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  is a monovalent organic group; A is a monovalent group showing acidity; and n is an integer of 1 or 2, and a siloxane-containing polyamide acid, having repeating units represented by the formulae (24): ##STR98## wherein R 1  is a divalent organic group having 4 or more carbon atoms; R 11  is a divalent organic group having one or more siloxane skeletons; R 12  is a divalent organic group having one or more siloxane skeletons; and R 13  is a divalent organic group having one or more aromatic groups, wherein the polyimide precursor is contained in an amount of 70 to 99 parts by weight, and the polyamide acid is contained in an amount of 1 to 30 parts by weight. 
     
     
       36. A polyimide precursor composition according to claim 35, wherein the siloxane-containing polyamide acid further has repeating units of the formula: ##STR99## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; and R 13  is a divalent organic group containing two or more aromatic rings, the number of repeating units of the formula (24) being 1 or more, and the number of repeating units of the formula (25) being 99 or less, when a total of the repeating units of the formulae (24) and (25) is 100. 
     
     
       37. A polyimide precursor composition according to claim 35, wherein R 11  is one member selected from the following formulae: ##STR100## and R 12  is one member selected from the following formulae: ##STR101## wherein n is an integer of 2 to 12. 
     
     
       38. A polyimide precursor composition comprising a polyimide precursor having repeating units of the formula: ##STR102## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; R 2  is a trivalent or tetravalent organic group containing one or more aromatic rings; R 3  is (a) a group represented by the formula: ##STR103## wherein R 5 , R 6  and R 7  are independently a hydrogen atom, an alkyl group, a phenyl group, a vinyl group, or a propenyl group; and R 8  is a divalent organic group, or a combination of (a) and (b) an alkyl group having 1 to 6 carbon atoms; A is a monovalent group showing acidity; and n is an integer of 1 or 2, and further having repeating units of the formula: ##STR104## wherein R 1  is as above; R 3  is a monovalent organic group; and R 4  is a divalent organic group containing one or more aromatic rings or silicon atoms, the number of repeating units of the formula (1) being 10 or more, and the number of repeating units of the formula (2) being 90 or less, when a total of repeating units of the formulae (1) and (2) is 100, wherein the polyimide precursor is contained in an amount of 70 to 99 parts by weight, and a siloxane-containing polyamide acid having repeating units represented by the formula (24): ##STR105##  wherein R 1  is as above; R 11  is a divalent organic group having one or more siloxane skeletons; R 12  is a divalent organic group having one or more siloxane skeletons; and R 13  is a divalent organic group having one or more aromatic rings, is also contained in an amount of 1 to 30 parts by weight.   
     
     
       39. A polyimide precursor composition according to claim 38, wherein the siloxane-containing polyamide acid further has repeating units of the formula: ##STR106## wherein R 1  is a tetravalent organic group having 4 or more carbon atoms; and R 13  is a divalent organic group containing two or more aromatic rings, the number of repeating units of the formula (24) being 1 or more, and the number of repeating units of the formula (25) being 99 or less, when a total of the repeating units of the formulae (24) and (25) is 100.